Post on 24-Feb-2016
description
Sacrificial Agent for Reducing Adsorption
of Anionic Surfactants
By: Hadi ShamsiJazeyi, George J. Hirasaki, Rafael Verduzco
Rice UniversityChemical and Bio-molecular Engineering Department
17th Annual Meeting of Rice University Consortium for Process in Porous Media
April 29, 2013
Conclusions
Results and Discussions
Materials and Methods
Problem Definition
Why Sodium Polyacrylate? Any role for Mw of polyacrylate?
Does polyacrylate reduce adsorption of different anionic surfactants on
different rocks and minerals?
Effect of salinity and divalent ions on application of polyacrylate as
sacrificial agent.
What is the adsorption of polyacrylate in comparison with anionic surfactant?
Experimental Evidence for the effect of anhydrite on adsorption of anionic
surfactants?
How does application of polyacrylate affect the total material cost?
How dynamic and static adsorption tests compares?
Anhydrite reacts with Sodium Carbonate! Can Polyacrylate be used?
2
Adsorption of anionic surfactant on a positively-charged surface of
rock/mineral
First-layer adsorption is governed by electrostatics
Second-Layer adsorption can happen at high concentrations
Anhydrite reacts with Sodium Carbonate! Can Polyacrylate be used?
2
Adsorption of anionic surfactant can be decreased by turning the surface
charge negative when an alkali is used to raise the pH above pHpzc
Anhydrite reacts with Sodium Carbonate! Can Polyacrylate be used?
2
Anhydrite reacts with Sodium Carbonate! Can Polyacrylate be used?
2
Conclusions
Results and Discussions
Materials and Methods
Introduction and Problem Definition
Why Sodium Polyacrylate? Any role for Mw of polyacrylate?
Does polyacrylate reduce adsorption of different anionic surfactants on
different rocks and minerals?
Effect of salinity and divalent ions on application of polyacrylate as
sacrificial agent.
What is the adsorption of polyacrylate in comparison with anionic surfactant?
Experimental Evidence for the effect of anhydrite on adsorption of anionic
surfactants?
How does application of polyacrylate affect the total material cost?
How dynamic and static adsorption tests compares?
List of surfactants
Trade or descriptive
nameChemical structure Activity
(%) Supplier
Neodol-67(N) bC16-17(CH3-CH-CH2-O)7-SO4Na 22.88 STEPAN
IOS15-18(I)
R-CH(OH)-CH2-CH(SO3)-R (~75%)R-CH=CH-CH(SO3-)-R
(~25%)where R+R’ = C12-15
21.29 STEPAN
NI-BlendA Blend of Neodol-67-7PO-Sulfate
and IOS15-18 (N:I)=4:1
-- --
Petro-step S13B i-C13-(PO)7 –SO4Na 85.50 TIORCO
3
List of polyacrylatesTrade or
descriptive name
Chemical structure Activity (%) Supplier
FLOSPERSE 1000 Sodium Polyacrylate (Mw=2200 Da) 44 SNF
FLOSPERSE3000
Sodium Polyacrylate (Mw=4500 Da) 44 SNF
FLOSPERSE15000 Sodium Polyacrylate (Mw=150 KDa) 30 SNF
FLOPAMAN 995 BPM Sodium Polyacrylate (Mw~3 MDa) 100 SNF
ACUMER 1100 Sodium Polyacrylate (Mw=4500 Da) 47-49 DOW Chem.
Poly(acrylic sodium salt) Sodium Polyacrylate (Mw= 5100 Da) 100 Sigma-
Aldrich
4
Measurement of Adsorption
Plateau region of adsorption isotherms should be measured.
Both initial and equilibrium concentrations are measured.
Equilibrium concentration should be far enough from initial concentration,
so that the noise in measurement can be neglected.
Concentration of anionic surfactant is measured using potentiometric titration.
Concentration of sodium polyacrylate is measured using a colorimetric method.5
Conclusions
Results and Discussions
Materials and Methods
Introduction and Problem Definition
Why Sodium Polyacrylate? Any role for Mw of polyacrylate?
Does polyacrylate reduce adsorption of different anionic surfactants on
different rocks and minerals?
Effect of salinity and divalent ions on application of polyacrylate as
sacrificial agent.
What is the adsorption of polyacrylate in comparison with anionic surfactant?
Experimental Evidence for the effect of anhydrite on adsorption of anionic
surfactants?
How does application of polyacrylate affect the total material cost?
How dynamic and static adsorption tests compares?
Anhydrite Can Affect Sodium Carbonate and Increase Adsorption of Anionic Surfactant
0.0 0.1 0.2 0.3 0.4 0.50
1
2
3
4
5
6
7
8
9
10
Equilibrium Concentration (wt%)
Adso
rptio
n (m
g/g)
Adsorption of NI-Blend, Initial Con-centration of NI-Blend = 0.5 %
3.5 % NaCl Salinity, Room Tem-perature, 24 h Equilibrium Time
2.6
1.3
0.9SAR=0.6
SAR=0.70.8
1.22.5
1% Sodium Carbonate + Pure Calcite (SAR=∞)
Variable SAR (24 h Eq. time)
Variable SAR (72 h Eq. time)
Pure Calcite + 5 % AnhydriteNo Sacrificial Agent
(SAR=0)
6
SAR = (# of moles of sodium carbonate) / (# of moles of anhydrite)
Conclusions
Results and Discussions
Materials and Methods
Introduction and Problem Definition
Why Sodium Polyacrylate? Any role for Mw of polyacrylate?
Does polyacrylate reduce adsorption of different anionic surfactants on
different rocks and minerals?
Effect of salinity and divalent ions on application of polyacrylate as
sacrificial agent.
What is the adsorption of polyacrylate in comparison with anionic surfactant?
Experimental Evidence for the effect of anhydrite on adsorption of anionic
surfactants?
How does application of polyacrylate affect the total material cost?
How dynamic and static adsorption tests compares?
Characterization of the Rocks/Minerals
Adsorbent (Powdered
Rock/Mineral)
Multi-point BET
Surface Area* (m2/g)
T-Method External
Surface Area (m2/g)
T-Method Micro-Porous Pore Volume
(cc/g)
Average Pore
Diameter (nm)
Anhydrite Percentage
(%)Other Notes
purified calcite 1.318 1.222 5.008E-5 1.820 0.07
(99.5 wt% CaCO3)Alfa Aesar
[Lot # C270009]
industrial calcite 1.608 1.297 1.617E-5 1.780 0.11
97.00 wt% CaCO3
(38.80 wt% Ca)Franklin Industrial
Minerals
Carlpool dolomite 0.7846 0.7426 1.726E-5 4.181 1.76
(20.00 wt% Ca)(10.00 wt% Mg)
Earthsafe Organics
Carlpool Products
Indiana limestone 0.9851 0.9850 1.421E-7 4.363 0.82 Kocurek Industries
purified kaolinite 20.8655 19.5626 5.832E-4 4.969 0.03 Sigma-Aldrich
[Lot # 048K0046]
powdered Berea
sandstone2.6750 2.6730 3.341E-4 1.149 NA Kocurek Industries
7
Polyacrylate vs. Sodium Carbonate for Reducing Adsorption of NI-Blend on Different Rocks/Minerals
Carlpool Dolomite
Franklin In-dustrial Calcite
Kaolinite Indiana LimeStone
Powderized Berea
Sandstone
0
1
2
3
4
5
6
7
8 W/O Sacrificial Agent
After Addition of 1 wt % Na2CO3
After Addition of 2500 ppm of Sodium Polyacrylate (4500 Da)
Ads
orpt
ion
(mg/
g)
Room Temperature, 24 h Equilibrium time
Initial Concentration of NI-Blend = 0.5 wt%
Rotary Mixer (4-5 rpm)
up to
18
Almost Zero Adsorption after addition of 2500 ppm
Na-Polyacrylate
8
Reducing Adsorption of Two Different Surfactants using Polyacrylate on Carlpool Dolomite
0 500 1000 1500 2000 2500 30000
0.5
1
1.5
2
2.5
NI-Blend
S13B
Initial Concentration of Sodium Polyacrylate (Mw=4500 Da) (ppm)
Ads
orpt
ion
(mg/
g)
NI-Blend S13B0
0.5
1
1.5
2
2.5
Without Sacrificial Agent
After adding 2500 ppm Sodium Polyacrylate (Mw=4500 Da)
Ads
orpt
ion
(mg/
g)
9
Conclusions
Results and Discussions
Materials and Methods
Introduction and Problem Definition
Why Sodium Polyacrylate? Any role for Mw of polyacrylate?
Does polyacrylate reduce adsorption of different anionic surfactants on
different rocks and minerals?
Effect of salinity and divalent ions on application of polyacrylate as
sacrificial agent.
What is the adsorption of polyacrylate in comparison with anionic surfactant?
Experimental Evidence for the effect of anhydrite on adsorption of anionic
surfactants?
How does application of polyacrylate affect the total material cost?
How dynamic and static adsorption tests compares?
Reducing Adsorption of NI-Blend on Carlpool Dolomite: Polyacrylate vs. Different Chemicals
10
Glyceri
c acid
Glycolic
acid
Sodium carbonate
Sodium EDTA
Pectin
Mw=2
MDa
Sodium alginate
Mw=2
MDa
Sigma Na-p
olyacry
late M
w=210
...
Dow Na-polya
crylat
e Mw=2
100 D
a
Sigma Na-p
olyacry
late M
w=510
...
Dow Na-polya
crylat
e Mw=4
100 D
a0.0
0.4
0.8
1.2
1.6
2.0A
dsor
ptio
n of
NI-B
lend
(mg/
g) Monomer Sacrificial Agents Polymeric Sacrificial Agents
Sodium polyacrylates with different Mw from different
vendors
Sodium Polyacrylate vs. Other Sacrificial Agents in the Literature
11
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 10.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0Poly(EthyleneGlycol) Methyl Ether (Mw=5000 Da)
Sodium Metaborate
sodium carbonate
Sodium Polyacrylate (Mw=4500 Da)
Concentration of added Sacrificial Agent (wt %)
Adso
rptio
n of
NI-B
lend
on
Carlp
ool d
olom
ite
(mg/
g)
Conclusions
Results and Discussions
Materials and Methods
Introduction and Problem Definition
Why Sodium Polyacrylate? What is role for Mw of polyacrylate?
Does polyacrylate reduce adsorption of different anionic surfactants on
different rocks and minerals?
Effect of salinity and divalent ions on application of polyacrylate as
sacrificial agent.
What is the adsorption of polyacrylate in comparison with anionic surfactant?
Experimental Evidence for the effect of anhydrite on adsorption of anionic
surfactants?
How does application of polyacrylate affect the total material cost?
How dynamic and static adsorption tests compares?
Effect of Molecular Weight of Polyacrylate on adsorption of anionic surfactant
12
0 500 1000 1500 2000 25000.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
Sodium Propionate (Repeating Unit of Sodium Polyacrylate)
SNF FLOSPERSE 1000 (Sodium Polyacrylate Mw=2200 Da)
SNF FLOSPERSE 3000 (Sodium Polyacrylate Mw=4500 Da)
SNF FLOSPERSE 15000 (Sodium Polyacrylate Mw=150,000 Da)
SNF FLOPAM AN 995 BPM (Sodium Polyacrylate Mw=2.5-3.5 M Da)
Initial Concentration of Sacrificial Agents Added (ppm)
Adso
rptio
n of
NI-B
lend
(mg/
g)
Conclusions
Results and Discussions
Materials and Methods
Introduction and Problem Definition
Why Sodium Polyacrylate? What is role for Mw of polyacrylate?
Does polyacrylate reduce adsorption of different anionic surfactants on
different rocks and minerals?
Effect of salinity and divalent ions on application of polyacrylate as
sacrificial agent.
What is the adsorption of polyacrylate in comparison with anionic surfactant?
Experimental Evidence for the effect of anhydrite on adsorption of anionic
surfactants?
How does application of polyacrylate affect the total material cost?
How dynamic and static adsorption tests compares?
Adsorption of Polyacrylate (Mw=4500Da) on Carlpool Dolomite
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
Adso
rptio
n (m
g/g)
Initial Concentration of Polymer = 0.5 %wtInitial Concentration of Surfactant VariesAll solution @ 3.5 % NaCl, Room TemperatureDolomite (from Carlpool) 20% Ca, 10% Mg
Compare Adsorption of NI-Blend and that of Sodium Polyacrylate
(Mw=4500Da) on the same Adsor-bent (Carlpool Dolomite)
Polyacrylate Adsorption
NI-Blend Adsorption
13
Conclusions
Results and Discussions
Materials and Methods
Introduction and Problem Definition
Why Sodium Polyacrylate? What is role for Mw of polyacrylate?
Does polyacrylate reduce adsorption of different anionic surfactants on
different rocks and minerals?
Effect of salinity and divalent ions on application of polyacrylate as
sacrificial agent.
What is the adsorption of polyacrylate in comparison with anionic surfactant?
Experimental Evidence for the effect of anhydrite on adsorption of anionic
surfactants?
How does application of polyacrylate affect the total material cost?
How dynamic and static adsorption tests compares?
Effect of salinity
NI-Blend AdsorptionPowdered Berea Sandstone
NI-Blend Adsorption Carlpool Dolomite
0 1 2 3 40.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
No sacrificial agent added
After addition of 2500 ppm sodium polyacrylate (Mw=4500 Da)
NaCl Salinity (wt %)
Ads
orpt
ion
of N
I-Ble
nd o
n C
arlp
ool
Dol
omite
(mg/
g)0.5 1 1.5 2 2.5 3 3.5 4
0
0.5
1
1.5
2
2.5
No sacrificial agent added
After addition of 2500 ppm sodium polyacrylate (Mw=4500 Da)
NaCl Salinity (wt %)
Adso
rptio
n of
NI-B
lend
on
Pow
dere
d Be
rea
Sand
ston
e (m
g/g)
14
Effect of divalent ions
NI-Blend Adsorption Kaolinite
NI-Blend Adsorption Pure Calcite
0 1000 2000 30000.0
0.5
1.0
1.5
2.0
2.5
3.0
3.5
4.0
4.5
5.0
On Pure Calcite W/O Sacrificial Agent On Pure Calcite W/ 2500 ppm Sodium Polyacry-late (4500 Da)
Concentration of Added CaCl2 (ppm)
NI-B
lend
Ads
orpt
ion
(mg/
g)
Initi
al S
olut
ion
Bec
omes
Haz
y
15
0 500 1000 1500 2000 2500 3000 35000
5
10
15
20
25
30 On Pure Kaolinite W/O Sacrificial Agent On Pure Kaolonite W/ 2500 ppm Sodium Polyacrylate (4500 Da)
Concentration of added CaCl2 (ppm)
NI-B
lend
Ads
orpt
ion
(mg/
g)
Initi
al S
olut
ion
beco
mes
Haz
y
Effect of divalent ions
NI-Blend Adsorption on Powdered Berea Sandstone
NI-Blend Adsorption on Carlpool Dolomite
0 1000 2000 30000
1
2
3
4
5On Powdered Berea Sandstone W/O Sacrificial Agent
On Powdered Berea Sandstone W/ 2500 ppm Sodium Polyacrylate (4500 Da)
Concentration of Added CaCl2 (ppm)
NI-B
lend
Ads
orpt
ion
(mg/
g)
Initi
al S
olut
ion
Bec
omes
Haz
y
0 1000 2000 30000.0
0.5
1.0
1.5
2.0
2.5
3.0On Carlpool Dolomite W/O Sacri-ficial Agent On Carlpool Dolomite W/ 2500 ppm Sodium Polyacrylate (4500 Da)
Concentration of Added CaCl2 (ppm)
NI-B
lend
Ads
orpt
ion
(mg/
g)
Initi
al S
olut
ion
Bec
omes
Haz
y
16
Conclusions
Results and Discussions
Materials and Methods
Introduction and Problem Definition
Why Sodium Polyacrylate? What is role for Mw of polyacrylate?
Does polyacrylate reduce adsorption of different anionic surfactants on
different rocks and minerals?
Effect of salinity and divalent ions on application of polyacrylate as
sacrificial agent.
What is the adsorption of polyacrylate in comparison with anionic surfactant?
Experimental Evidence for the effect of anhydrite on adsorption of anionic
surfactants?
How does application of polyacrylate affect the total material cost?
How dynamic and static adsorption tests compares?
Economical Study: Effect of Reservoir/Injection (Alfa Dimensionless Number)
17
* *****
**
* *
Economical Study: Effect of Cost of Polyacrylate to Cost of Surfactant
Cost Dimensionless Number
18
*
** * * * * *
**
Conclusions
Results and Discussions
Materials and Methods
Introduction and Problem Definition
Why Sodium Polyacrylate? What is role for Mw of polyacrylate?
Does polyacrylate reduce adsorption of different anionic surfactants on
different rocks and minerals?
Effect of salinity and divalent ions on application of polyacrylate as
sacrificial agent.
What is the adsorption of polyacrylate in comparison with anionic surfactant?
Experimental Evidence for the effect of anhydrite on adsorption of anionic
surfactants?
How does application of polyacrylate affect the total material cost?
How dynamic and static adsorption tests compares?
Dynamic Adsorption of 0.5 wt% NI-blend on Carlpool Dolomite with no sacrificial agent
19
Dynamic Adsorption of 0.5 wt% NI-blend On Carlpool Dolomite with 1000 (ppm) sodium polyacrylate
20
Comparison of Static and Dynamic Adsorptions
0 ppm sodium polyacrylate
1000 ppm sodium polyacrylate
2500 ppm sodium polyacrylate
00.20.40.60.8
11.21.41.61.8
dynamic test static test
NI-B
lend
Ads
orpt
ion
(mg/
g)
0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5-0.10.40.91.41.92.42.93.43.94.4
Pure Calcite + 5% Anhydrite without Sacrificial Agent
Various PAR
Polyacrylate on Calcite no an-hydrite
Equilibrium Concentration of NI-blend (wt%)
NI-b
lend
Ads
orpt
ion
(m
g/g)
22
PAR = (# of repeating units in polyacrylate) / (# of moles of anhydrite)
Decrease in PAR
Conclusions
Results and Discussions
Materials and Methods
Introduction and Problem Definition
Why Sodium Polyacrylate? What is role for Mw of polyacrylate?
Does polyacrylate reduce adsorption of different anionic surfactants on
different rocks and minerals?
Effect of salinity and divalent ions on application of polyacrylate as
sacrificial agent.
What is the adsorption of polyacrylate in comparison with anionic surfactant?
Experimental Evidence for the effect of anhydrite on adsorption of anionic
surfactants?
How does application of polyacrylate affect the total material cost?
How dynamic and static adsorption tests compares?
1. Sodium polyacrylate strongly reduces adsorption of different anionic surfactants
on different rocks/minerals more than other traditional sacrificial agents even in
presence of anhydrite.
2. No high molecular weight polyacrylate to be used (4500 Da is enough).
3. Adsorption of sodium polyacrylate does NOT change with presence of anionic
surfactant, and is almost 1/4th of the adsorption of NI-Blend on same rock.
4. Effect of salinity and divalent ions in the brine was tested. In the absence of
anhydrite, sodium polyacrylate acts as a better sacrificial agent in purified water.
In the presence of anhydrite, purification of water does NOT add advantage.
5. By choosing the optimal concentration of polyacrylate the total material cost of a
dynamic injection can be significantly reduced.
23
Conclusion
THANK YOU
25
Back-Up Slides
26
Sodium Polyacrylate has negative charge in neutral pH
Surfactant has negative charge in neutral pH
Does this mean that Sodium Polyacrylate can interfere with
measuring concentration of anionic (sulfate-based)
surfactant?
Is Polyacrylate Affecting the titration of Surfactant?
27
Is Polyacrylate Affecting the titration of Surfactant?(…Continued)
40
Our strategy is to do the potentiometric titration at pH=3 so that the polyacrylate does not have any
charge, but sulfate-based anionic surfactant does.
-0.399999999999999 0.100000000000001 0.6000000000000010
1
2
3
4
5
6
7
f(x) = 10.9850243889184 xR² = 0.999426383953348
W/O PolymerLinear (W/O Polymer)W/ Polyacrylate
Sample Size (cc)
Volu
me
of ti
trant
use
d fo
r EP
(cc)
The surfactant used is S13B.Concentration of Surfactant = 0.75 %Concentration of Polymer Added =
0.56 %pH 3 was provided in the titration ex-
periment using HCl solution.The source of Polyacrylate is Acumer
1100.two solutions were made. The first
one has ~0.75% of surfactant at 3.5 % NaCl. The second one has ~0.75% of surfactant, ~0.56% of polymer at 3.5
% NaCl.Different sample sizes were taken
from these two solutions, diluted to about 30 (g) using DI-Water, and then
HCl was added and pH was mea-sured to be about 3. Then, titration
was done by potentiometric titration.
28
Measurement of Concentration of Sodium Polyacrylate(Colorimetric Method)
Effect of S13B On
Colorimetric
Measurement
29
Dynamic Adsorption of 0.5 wt% NI-blend on Carlpool Dolomite with 2500 (ppm) sodium polyacrylate
21